Phosphonic polymers having a phosphinate backbone and methods of making and using thereof

Abstract

Described herein are new phosphonic polymers and methods of making and using the same. The polymers are prepared by the polymerization of phosphonic acid monomers with hypophosphorous acid, an alkali metal hypophosphite, an alkyl substituted hypophosphite, or any combination thereof. The resultant polymers have pendant phosphonate groups attached to the polymer backbone as well as phosphinate groups incorporated within the polymer backbone. Additional monomers can be used to produce copolymers, terpolymers, and the like. The polymers described herein have numerous applications with respect to inhibiting scale formation and corrosion in a number of systems.

1. A polymer produced by the process comprising polymerizing a monomer comprising the formula I, a dimer comprising the formula IV, or a combination thereof 
       
         
           
           
               
               
           
         
       
       wherein R 1 -R 4  and R 7  comprises, independently, hydrogen, an alkyl group, a cycloalkyl group, a heteroalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, a protecting group, or a combination thereof, or R 2  and R 4  form a substituted or unsubstituted cycloalkyl group, with hypophosphorous acid, an alkali metal hypophosphite, an alkyl substituted hypophosphite, or any combination thereof. 
     
     
       2. The polymer of  claim 1 , wherein R 2  and R 3  comprises hydrogen. 
     
     
       3. The polymer of  claim 2 , wherein R 1  and R 7  are hydrogen. 
     
     
       4. The polymer of  claim 3 , wherein R 4  comprises an aryl group or a heteroaryl group. 
     
     
       5. The polymer of  claim 3 , wherein R 4  comprises a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group. 
     
     
       6. The polymer of  claim 3 , wherein R 4  comprises CH 2 C 6 H 4 -p-S(O) 2 OH or an alkali salt thereof. 
     
     
       7. The polymer of  claim 1 , wherein R 1 -R 4  and R 7  are hydrogen. 
     
     
       8. The polymer of  claim 7 , wherein R 4  comprises an alkyl group. 
     
     
       9. The polymer of  claim 8 , wherein the alkyl group comprises methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, or hexyl. 
     
     
       10. The polymer of  claim 7 , wherein R 4  comprises a cycloalkyl group, and the cycloalkyl group comprises cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. 
     
     
       11. The polymer of  claim 1 , wherein the cycloalkyl group comprises cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. 
     
     
       12. The polymer of  claim 1 , wherein R 4  comprises a higher alkyl group. 
     
     
       13. The polymer of  claim 12 , wherein the higher alkyl group comprises heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, or tetracosyl. 
     
     
       14. The polymer of  claim 1 , wherein at least one of R 2 , R 3 , or R 4  comprises a higher alkyl group, a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, a protecting group, or an aryl group substituted with one or more SO 2 R or S(O) 2 OR groups, where R is hydrogen, an alkali metal, or an alkyl group. 
     
     
       15. The polymer of  claim 1 , wherein the polymer comprises the polymerization product of two or more different monomers comprising the formula I. 
     
     
       16. The polymer of  claim 1 , wherein the polymer comprises the polymerization product between at least one monomer having the formula I and one or more olefinically unsaturated monomers. 
     
     
       17. The polymer of  claim 16 , wherein the olefinically unsaturated monomer comprises acrylic acid, methacrylic acid, acrylamide, methyl methacrylate, ethyl acrylate, 2-hydroxy ethyl acrylate, 2-hydroxy propyl acrylate, maleic acid, maleic anhydride, t-butylacrylamide, vinyl sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid (AMPS), styrene sulfonic acid or sodium salt thereof, vinyl acetate, styrene acetate, styrene benzoic acid, vinyl cyclopropane, vinyl cyclopentane, sodium vinyl sulfonate, vinyl cyclohexane, or any combination thereof. 
     
     
       18. The polymer of  claim 1 , wherein the alkali metal hypophosphite comprises sodium hypophosphite. 
     
     
       19. The polymer of  claim 1 , wherein the molar ratio of hypophosphorous acid, the alkali metal hypophosphite, or a combination thereof per monomer is from 1:5 to 1:50. 
     
     
       20. The polymer of  claim 1 , wherein the molar ratio of hypophosphorous acid, the alkali metal hypophosphite, or a combination thereof per monomer is from 1:5 to 1:25. 
     
     
       21. The polymer of  claim 1 , wherein the polymer comprises the polymerization product between at least one monomer having the formula I and at least one cyclic vinyl phosphonic acid or ester thereof. 
     
     
       22. A method for producing a polymer comprising polymerizing a monomer comprising the formula I, a dimer comprising the formula IV, or a combination thereof 
       
         
           
           
               
               
           
         
       
       wherein R 1 -R 4  and R 7  comprises, independently, hydrogen, an alkyl group, a cycloalkyl group, a heteroalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, a protecting group, or a combination thereof, or R 2  and R 4  form a substituted or unsubstituted cycloalkyl group, with hypophosphorous acid, an alkali metal hypophosphite, or a combination thereof. 
     
     
       23. A method for inhibiting scale formation in a system comprising applying to the system the polymer of  claim 1 . 
     
     
       24. A method for inhibiting corrosion in a system comprising applying to the system the polymer of  claim 1 . 
     
     
       25. A method for inhibiting corrosion and scale formation in a system comprising applying to the system the polymer of  claim 1 .